WO2007052447A1 - 樹脂被覆金属顔料およびその製造方法、ならびにこれを用いた水性塗料 - Google Patents
樹脂被覆金属顔料およびその製造方法、ならびにこれを用いた水性塗料 Download PDFInfo
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- WO2007052447A1 WO2007052447A1 PCT/JP2006/320255 JP2006320255W WO2007052447A1 WO 2007052447 A1 WO2007052447 A1 WO 2007052447A1 JP 2006320255 W JP2006320255 W JP 2006320255W WO 2007052447 A1 WO2007052447 A1 WO 2007052447A1
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- metal pigment
- resin
- phosphate ester
- solvent
- pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/644—Aluminium treated with organic compounds, e.g. polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Definitions
- Resin-coated metal pigment method for producing the same, and aqueous coating using the same
- the present invention relates to a resin-coated metal pigment contained in a metallic paint used for coating metal or plastic, and more particularly, an excellent paint when used as an aqueous paint.
- the present invention relates to a resin-coated metal pigment having storage stability, particularly water resistance, and excellent chemical resistance when formed into a coating film.
- Patent Document 1 discloses an organic phosphate ester having a saturated aliphatic group and a V ⁇ ester residue containing an unsaturated aliphatic group and an ester containing an unsaturated aliphatic group. It has been proposed to use a mixture with an organophosphate having a residue as a pigment component.
- Patent Document 2 proposes coating the surface of aluminum flakes with a molybdate coating.
- Patent Document 3 a film derived from molybdenum peroxide is formed, and at least one amine selected from strong alkylamine, arylamine, alkanolamine, and alkoxylamine is selected.
- Aluminum pigments have been proposed. [0004] The metal pigment obtained by these techniques is excellent in storage stability as a water-based paint, but has poor chemical resistance when used as a coating film. However, this method is limited only to the case where the material is applied.
- Patent Document 4 describes trimethylolpropane tritalylate and / or trimethylolpropane trimetatalylate, a small amount of acrylic acid and Z or methacrylic acid. Metal powders coated with these copolymers have been proposed. Japanese Patent Publication No.
- Patent Document 5 describes radically polymerizable unsaturated carboxylic acids and three mono- or diester phosphates having radically polymerizable double bonds and radically polymerizable double bonds. It has the above-mentioned monomer strength. It is characterized in that it is tightly adhered and surface-coated by highly generated three-dimensional rosin, and has an alkali resistance of 1.0 or less and does not substantially aggregate in a heat stability test. A resin-coated metal pigment has been proposed.
- JP-A-64-040566 Patent Document 6) describes a copolymer obtained by reacting at least two selected groups consisting of an oligomer and a monomer having at least one polymerizable double bond.
- Patent Document 7 describes a monomer having a surface force polymerizable double bond of a raw material aluminum pigment, a monomer having one polymerizable double bond and one benzene ring, and ) A resin-coated aluminum pigment coated with a copolymer obtained by polymerizing acrylic acid has been proposed.
- Patent Document 8 As surface treatment technology having both water resistance and chemical resistance, International Publication No. WO96Z03 8506 pamphlet (Patent Document 8) includes (A) radical polymerizable unsaturated carboxylic acid, and And z or a phosphoric acid or phosphonic acid mono- or diester having a radically polymerizable double bond, and z or at least one coupling agent having a radically polymerizable double bond, and (B) a radical Using a monomer having three or more polymerizable double bonds and (C) a polymerization initiator, first, after adding (A) and treating the metal pigment, there are few (B) and (C).
- Patent Document 9 a metal pigment produced by a physical vapor deposition film crushing method is dispersed in an organic solvent, and then (A) radical polymerizable unsaturated carboxylic acid, radical polymerizable Phosphoric acid or phosphonic acid mono or diester having a double bond, coupling agent power having a radical polymerizable double bond is added, and (B) 3 or more radical polymerizable double bonds are added. Proposed a resin-coated metal pigment obtained by adding a monomer and (C) a polymerization initiator, and then gradually adding at least one of (B) and (C) and polymerizing. It has been.
- the water resistance is 50 using a paint adjusted to pH 9.5. Evaluation is based on the amount of gas generated in C and 24 hours. Under these conditions, the alkali resistance is substantially evaluated. Therefore, a proper water resistance evaluation is not performed.
- the pH of water-based paints in recent years is generally about 7.5 to 8.8, and water resistance is generally evaluated by gas generation within at least several days.
- Patent Document 1 JP-A-2-120368
- Patent Document 2 JP-A-6-57171
- Patent Document 3 International Publication No. WO02Z031061 Pamphlet
- Patent Document 4 JP-A 62-081460
- Patent Document 5 Japanese Patent Publication No. 01-049746
- Patent Document 6 Japanese Patent Laid-Open No. 64-040566
- Patent Document 7 Japanese Patent Laid-Open No. 2005-146111
- Patent Document 8 International Publication No. WO96Z038506 Pamphlet
- Patent Document 9 Japanese Unexamined Patent Publication No. 2000-044835
- the present invention solves the above-mentioned problems, makes it possible to improve the paint stability of water-based paints, particularly water resistance, and practically uses the chemical resistance of a coating film formed by coating the water-based paint. It is an object of the present invention to provide a resin-coated metal pigment that can be secured at a sufficiently high level, and a highly versatile, low-pollution water-based paint using the resin-coated metal pigment.
- a solution of a phosphate ester component (A) containing a phosphate mono- and Z- or diester having a radical polymerizable double bond, or a phosphate ester component (A) is dispersed in a solvent.
- An adsorption process for preparing a phosphate ester-adsorbing metal pigment formed by contacting a phosphoric acid ester on the surface of the metal pigment by bringing the resulting dispersion into contact with the metal pigment; and a phosphate ester-adsorbing metal pigment in the polymerization solvent A slurry preparation step of preparing a polymerization slurry in which a monomer having at least one polymerizable double bond and a polymerization component (B) having Z or oligomer power are dissolved in a polymerization solvent, A coating process for forming a resin coating layer on the surface of the phosphate ester adsorbing metal pigment by polymerizing component (B), wherein the dispersion comprises: First A solution obtained by dissolving the phosphate ester component (A) in the solvent of (2) is mixed with the second solvent, and the polymerization solvent has a solubility of 25 ° for the phosphate ester component (A) in the solvent lOOg.
- the slurry preparation step includes a step of preparing a pigment slurry in which the phosphate ester adsorbing metal pigment is dispersed in a polymerization solvent, and a step of mixing the polymerization component (B) with the pigment slurry.
- the present invention relates to a method for producing a resin-coated metal pigment.
- the present invention also relates to a method for producing a resin-coated metal pigment further comprising a step of polymerizing a phosphate ester adsorbed on a phosphate ester adsorbing metal pigment after the adsorption step.
- the present invention also relates to a method for producing a resin-coated metal pigment in which a polar solvent is used as a solvent in the solution of the phosphate ester component (A).
- the same solvent may be used as the second solvent and the polymerization solvent.
- the present invention relates to a method for producing a fat-coated metal pigment.
- the present invention also relates to a method for producing a resin-coated metal pigment which is a phosphate ester component (A) force 2-methacryloyloxetyl acetic acid phosphate.
- the present invention also provides that the phosphorous content metal pigment has a phosphorus content per unit surface area of 0.05 to L
- the present invention relates to a method for producing a resin-coated metal pigment in the range of 3 mg / m 2 .
- the present invention also relates to a method for producing a resin-coated metal pigment in which the polymerization component (B) comprises a monomer having at least two polymerizable double bonds.
- the present invention further relates to a resin-coated metal pigment having a metal pigment, a phosphate ester layer, and a resin coating layer that covers the metal pigment via the phosphate ester layer.
- the phosphor layer is a phosphate mono- and Z- or diester having a radical polymerizable double bond, or a homopolymer or copolymer of mono- and z- or diester phosphate
- the resin coating layer is at least 1 Monomer or copolymer obtained by polymerization of a monomer having one polymerizable double bond and Z or oligomer, and the phosphorus content per unit surface area of the resin-coated metal pigment is 0.05.
- a resin-coated metal pigment in the range of L 3 mgZm 2 .
- the present invention also relates to a resin-coated metal pigment which is a phosphate ester layer strength 2-methacryloyloxetyl acetic acid phosphate.
- the present invention further relates to a water-based paint containing the above-mentioned resin-coated metal pigment and a binder.
- a resin coating capable of achieving both storage stability when used in water-based paints, in particular, water resistance and chemical resistance of a coating film at a practically sufficient level. It is possible to provide a metal face.
- FIG. 1 is a diagram showing an outline of an apparatus used for measuring a hydrogen gas generation amount.
- FIG. 2 is a graph showing the relationship between Log (elapsed time) (seconds) measured by the apparatus shown in FIG. 1 and the amount of gas generated.
- the method for producing a resin-coated metal pigment according to the present invention is characterized in that the resin-coated layer is formed after the radical polymerizable double bond phosphate is uniformly adsorbed on the surface of the metal pigment. And a solution of the phosphoric acid ester component (A) containing a phosphoric acid mono- and Z- or diester having a radical polymerizable double bond, or a dispersion liquid in which the phosphoric acid ester component (A) is dispersed in a solvent.
- the resin coating layer is formed after the phosphate ester is adsorbed on the surface of the metal pigment.
- the phosphoric acid ester used in the present invention acts as a corrosion inhibitor on the surface of the metal pigment, and the resin coating layer used in the present invention has an effect of improving the chemical resistance of the metal pigment. Therefore, the phosphate ester is uniformly adsorbed on the surface of the metal pigment, and the resin coating layer is uniformly formed on the phosphate ester-adsorbed metal pigment, thereby providing good water resistance when made into a paint.
- a resin-coated metal pigment that imparts good chemical resistance when formed into a coating film can be obtained.
- the phosphate ester component (A) used in the present invention is adsorbed on the surface of the metal pigment by the adsorption action of the OH group in the molecule on the surface of the metal pigment.
- the phosphoric acid ester component (A) used in the present invention has a radical polymerizable double bond, and the polymerization component (B) used in the present invention has at least one polymerizable double bond. . Therefore, the phosphate ester adsorbed on the surface of the metal pigment in the adsorption step forms a covalent bond with the polymerization component (B) in the subsequent coating step, so that the metal pigment is passed through the phosphate ester. The effect that the strong adhesiveness of a coconut resin coating layer is expressed is acquired. [0028] ⁇ Adsorption process>
- a solution of the phosphate ester component (A) or a dispersion in which the phosphate ester component (A) is dispersed in a solvent is brought into contact with the metal pigment.
- the dispersion is obtained by mixing a solution obtained by dissolving the phosphate ester component (A) in the first solvent with the second solvent.
- the phosphate ester component (A) can be finely dispersed in the dispersion. That is, in the present invention, the phosphate ester component (A) can be uniformly adsorbed on the surface of the metal pigment by contacting the metal pigment in a dissolved or finely dispersed state.
- metal pigments are often sold in a paste state containing a solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon alone or two or more of these solvents as a mixed solvent.
- solvents generally do not dissolve phosphate mono- or diesters having radically polymerizable double bonds, but are solvents (non-solvents) or dissolve but have low solubility, and are generally solvents (poor solvents). It is.
- a solvent in the metal facial paste is used as a solvent for dissolving the phosphate ester component (A). And then kneading after adding the phosphate ester component (A).
- the phosphate ester component (A) may be added as it is, or may be diluted with a solvent that dissolves the phosphate ester component (A) and then added.
- a method of diluting the metal pigment paste with a solvent that dissolves the phosphate ester component (A) and then adding the phosphate ester component (A) and kneading or stirring may be employed.
- the system contains an aliphatic hydrocarbon or aromatic hydrocarbon derived from a metal pigment paste or a mixed solvent thereof (that is, a poor solvent for the phosphate ester component (A)) and a phosphate ester component (A).
- the solvent to be dissolved that is, the good solvent of the phosphate ester component (A)
- the good solvent to be added so that the composition becomes a composition capable of dissolving the phosphate ester component (A). It is necessary to control the amount.
- the metal pigment paste was replaced with a good solvent for the phosphate ester component (A), and Thereafter, a method may be employed in which the metal pigment paste is dispersed in the good solvent to form a slurry, and the phosphate ester component (A) is added while stirring the resulting slurry.
- the next polymerization reaction may be carried out as it is, or the phosphate ester adsorbing metal pigment may be isolated in a paste form by filtration and supplied to the next step.
- a method is also adopted in which the metal pigment paste is dispersed in a good solvent of the phosphate ester component (A) as a slurry, and the phosphate ester component (A) is added while stirring the resulting slurry. obtain.
- the amount of the good solvent is adjusted so that the composition is a composition that dissolves the phosphate ester component (A). I need to control it.
- the slurry may be used for the next polymerization reaction as it is, or may be filtered to isolate the phosphate ester adsorbing metal pigment in the form of a paste.
- the adsorption step can be performed as follows.
- a solution obtained by dissolving the phosphate ester component (A) in the first solvent can be mixed with the second solvent to prepare a dispersion in which the phosphate ester component (A) is finely dispersed. That is, in this case, the first solvent is a good solvent for the phosphate ester component (A), and the second solvent is a poor solvent for the phosphate ester component (A) or the phosphate ester component (A). Do not dissolve! Use solvent.
- the metal pigment paste is replaced with a second solvent in advance, and then the metal pigment paste is dispersed in the second solvent to form a slurry, and the resulting phosphoric acid ester component (A) (A method of slowly adding a dispersion of A) or a solution comprising the phosphate ester component (A) and the first solvent over a period of 10 minutes or more can be employed. According to this method, the phosphate ester component (A) phase-separated in the second solvent is uniformly adsorbed on the entire surface of the metal pigment. Even after the adsorption process, the next polymerization reaction is carried out as it is, and the The acid ester adsorbing metal pigment may be isolated in paste form and supplied to the next step.
- the metal pigment paste is dispersed as it is in a second solvent to form a slurry, and the resulting slurry is stirred, while the dispersion of the phosphate ester component (A) or the phosphate ester component (A) and the first are mixed.
- a method of slowly adding a solution comprising the solvent 1 over a period of 10 minutes or more and adsorbing the phase-separated phosphate ester component (A) on the surface of the metal pigment can also be employed. In this method, since the poor solvent derived from the metal pigment paste and the second solvent coexist in the system, the composition becomes a composition that can maintain the finely dispersed state of the phosphate ester component (A).
- the slurry may be used for the next polymerization reaction as it is, or may be filtered to isolate the phosphate ester adsorbing metal pigment in the form of a paste.
- the excess phosphate ester component (A) is discharged out of the system together with the filtrate.
- the paste or slurry in which the phosphate ester component (A) is adsorbed to the metal pigment in the adsorption step described above is transferred to the next polymerization step.
- the paste or slurry obtained in the adsorption step may be used as it is, or the solvent may be substituted once and the force may be used.
- the added amount of the phosphate ester component (A) is larger than the saturated adsorption amount of the phosphate ester component (A) to the pigment particles, the obtained paste or slurry is !, and the phosphate ester component (A )
- the excessive amount of phosphate ester component (A) is phase-separated or precipitated and adsorbed onto the metal pigment, so it is not discharged out of the system even after filtration.
- the solvent may be replaced, or it may be a constraint on the next polymerization process.
- the present invention may further include a step of polymerizing the phosphate ester adsorbed on the phosphate ester adsorbing metal pigment after the above-described adsorption step.
- the phosphate ester can be more strongly adsorbed on the metal pigment surface.
- the phosphate ester component (A) is added to the first solvent or the second solvent as necessary.
- a dispersant may be added for the purpose of promoting fine dispersion of the component (A).
- Metal flakes such as aluminum, zinc, copper, bronze, nickel, titanium, stainless steel, and those alloy flakes are mentioned.
- aluminum flakes are particularly suitable because they are excellent in metallic brightness, are inexpensive and have a low specific gravity.
- the metal pigment used in the present invention is preferably in the form of flakes for use as a pigment for metallic paints, and the average particle diameter of the metal pigment is usually preferably about 1 to about LOO / zm. More preferably, it is 3-60 / ⁇ ⁇ . Further, the average thickness of the metal pigment is usually preferably about 0.01 to 5 / ⁇ ⁇ , more preferably 0.02 to 2 / ⁇ ⁇ .
- the average particle diameter of the metal pigment is 1 m or more, the metallic feeling or light is good, and when the average particle diameter is 100 / zm or less, the flake particles are difficult to protrude on the coating surface.
- the smoothness or sharpness of the image is good.
- the average thickness of the metal pigment is 0.01 ⁇ m or more, it is advantageous in that the strength is good and the workability during the manufacturing process is excellent, and the average thickness is 5 m. In the case of the following, it is advantageous in that the smoothness or sharpness of the coated surface is good and the production cost is low.
- the average particle size of the metal pigment is obtained by calculating a volume average from a particle size distribution measured by a known particle size distribution measurement method such as a laser diffraction method, a micromesh sieve method, or a Coulter counter method.
- the average thickness is calculated from the hiding power and density of the metal pigment.
- a grinding aid added during grinding may be adsorbed on the surface of the metal pigment used in the present invention.
- the grinding aid include fatty acids such as oleic acid and stearic acid, aliphatic amines, aliphatic amides, aliphatic alcohols and ester compounds. These have the effect of suppressing unnecessary acidity on the surface of the metal pigment and improving the gloss.
- the adsorption amount of the grinding aid is preferably less than 2 parts by mass per 100 parts by mass of the metal pigment. When the amount is less than 2 parts by mass, it is advantageous in that the surface gloss is hardly lowered.
- various colorants and color pigments can be adhered to the surface of the metal pigment.
- the colorant and the color pigment are not particularly limited. For example, quinacridone, diketopyrrolopyrrole, isoindolinone, indanthrone, perylene, perinone, anthraquinone, dixaxazine, benzimidazolone.
- the method for attaching the color pigment to the metal pigment used in the present invention is not particularly limited! However, after coating the color pigment with a dispersant, the mixture is stirred and mixed with the metal pigment in a nonpolar solvent. Thus, a method of attaching a color pigment to the metal pigment is preferable.
- dispersant examples include benzoic acid, vinyl benzoate, salicylic acid, anthrallic acid, m-aminobenzoic acid, p-aminobenzoic acid, 3-amino-4-methylbenzoic acid, and 3,4-diaminobenzoic acid.
- Acid p-aminosalicylic acid, 1 naphthoic acid, 2 naphthoic acid, naphthenic acid, 3 amino-2-naphthoic acid, kain cinnamate, amino cinnamate, and other aromatic carboxylic acids; ethylene diamine, trimethylene diamine, tetramethylene Diamine, pentamethylenediamine, hexamethylenediamine, 1,7 diaminoheptane, 1,8 diaminooctane, 1,10 diaminodecane, 1,12-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenol Direndiamine, 1,8 diaminonaphthalene, 1,2 diaminocyclohexane, stearyl propylene diamine, N- ⁇ - (amino (Noethyl) ⁇ -aminopropyltrimethoxysilane, N-j8- (
- an interference film or the like can be formed on the surface of the metal pigment.
- the method is not particularly limited.
- the metal pigment in order to form a light-interfering oxide film on the surface of individual particles of the metal pigment, the metal pigment is 300 to 700 in an atmosphere in which the amount of oxygen is controlled.
- a method of forming an air oxide film on the surface by heating to about ° C, or a method of coating a flake-shaped metal pigment with an oxide precursor such as a transition metal and thermally decomposing it is preferable.
- Phosphate component (A) In general, it is known that phosphoric acid or phosphoric acid mono- or diester acts as an adsorptive metal corrosion inhibitor by adsorbing on a metal surface. Phosphate component in the present invention
- the phosphoric acid mono- and Z- or diester having a radical polymerizable double bond used as (A) is a substance having both an adsorption type metal corrosion inhibitor function and radical polymerizability. It is considered that water resistance, which is one of the characteristics of the resin-coated metal pigment obtained in the present invention, can be achieved by uniformly adsorbing and polymerizing the phosphate ester component (A) on the surface of the metal pigment.
- Preferable examples of the phosphoric acid ester component (A) used in the present invention include 2-methacryloylloxichetila acid phosphate, di-2-methacryloyl oral chechetyla acid phosphate, tree 2-methacryloyloxetyl acetic acid phosphate, 2-acrylicyloxychetyl acid acid phosphate, di-2-atallyloyloxicyl acid acid phosphate, tri-one 2-atallyloyloxicyl acid acid phosphate , Diphenyl-2-L-methacryloyl Loxochetyl acid phosphate, Diphlo-Lu 2—Atariloy mushroom chilled acid phosphate, Dibutyl 2-dimethacryloyl Lochetyl acid acid phosphate, Dibutyl-2-Atalloy L'Ouchetil Azside Phosphate, Dioctyl 2-Mekakuri Irochechetilacidophosphate,
- the phosphoric acid ester component (A) include 2-methacryloyllochichetyl acidoside phosphate and 2-atallyloyllochichetyl acidoside phosphate as the phosphoric acid monoester. Of these, 2-methacryloyloxetyl acetic acid phosphate is particularly preferably used.
- the phosphate ester component (A) of the present invention may be composed only of phosphate mono- and Z- or di-esters having radical polymerizability, but it is free from radical polymerizable double bonds. Yes, and may further contain phosphate mono- and Z- or diesters.
- Examples of phosphoric acid mono- and Z- or diesters having no radically polymerizable double bond include, for example, methyl acid phosphate, ethyl acetate phosphate, butyl acid phosphate, Decyl azido phosphate, phenyl phosphonic acid, 2-ethyl hexyl acyl phosphate, lauryl atsido phosphate, stearyl azido phosphate, oleyl azido phosphate, dimethyl azido phosphate, jetyl azido phosphate Dibutyl acid phosphate, diisodecyl acid phosphate, di-2-ethylhexyl phosphate, dilauryl acid phosphate, distearyl acid phosphate, dioleyl acid phosphate, etc. It can be illustrated.
- a solvent that dissolves the phosphate ester component (A) is employed, and a single solvent or two or more solvents can be used.
- a mixed solvent may be used.
- the preferred solvent varies depending on the composition of the phosphate ester component (A), and therefore, an optimal solvent may be selected in combination with the phosphate ester component (A) to be used.
- the solvent that dissolves the phosphate ester component (A) is also limited to polar solvents, and ketones and alcohols are encouraged.
- polar solvents water and basic solvents are inappropriate.
- water when water is used, when an aluminum pigment or the like is used as a metal pigment, water reacts with aluminum to generate hydrogen gas.
- a basic solvent When a basic solvent is used, the basic solvent forms a salt with the acidic phosphoric acid unit, so that the phosphate ester component (A) is insoluble or the phosphate ester component (A ) May not be adsorbed.
- the above-mentioned solvent for example, those having an SP value in the range of 9.1 to 13, and further in the range of 9.2 to LO. 0 are preferably used. Those having an SP value within the above range are preferred because they are particularly excellent in the solubility of the phosphate ester component (A) used in the present invention.
- the SP value means a solubility parameter.
- a solvent in which 50 g or more of the phosphate ester component (A) is dissolved at 25 ° C with respect to the solvent lOOg is preferably used.
- the ester component (A) can be dissolved at an arbitrary ratio are also preferably used.
- a solution containing the phosphate ester (A) at a desired concentration can be prepared, and a sufficient amount of the phosphate ester can be adsorbed on the surface of the metal pigment.
- Preferable solvents include, for example, methanol, ethanol, 1 propanol, isopropyl alcohol, n-butanol, sbutanol, t-butanol, glycerin, allylic alcohol, ethylene glycol, ethylene glycol , Ethylene glycolenomonomethylenoateolene, ethyleneglycololemonomethoxymethylenoateol, ethylene glycol, acetone, acetylacetone, methyl ethyl ketone, jetyl ketone, cyclohexanone, diacetone alcohol, methyl isobutyl ketone, methyl Examples include n-butyl ketone, methyl-n-propyl ketone, and dimethyl sulfoxide.
- a solvent that can be a good solvent for the phosphate ester component (A) is preferably used V, and the same solvent as the solvent in the solution of the phosphate ester component (A) described above is preferably used.
- the second solvent examples include those capable of supplying a dispersion in which the phosphate ester component (A) is finely dispersed by mixing with the solution comprising the phosphate ester component (A) and the first solvent. Used. It is preferable that the second solvent does not substantially dissolve the phosphate ester component (A). More specifically, the solubility of the phosphate ester component (A) in the second solvent lOOg is 25 °. C is preferably 10 g or less.
- the SP value of the second solvent depends on the combination of the SP value of the first solvent that dissolves the phosphate ester component (A) and the use ratio, but it is within the range of 7.2 to 9.0. Furthermore, it is preferably within the range of 7.3 to 8.8. SP value force S7. If it is in the range of 2 to 9.0, the compatibility with the first solvent that dissolves the phosphate ester component (A) is good, and the dispersion of the phosphate ester component (A) Since the dispersion size in the inside becomes fine, the phosphate ester can be uniformly adsorbed on the surface of the metal pigment.
- the phosphate ester component (This is preferable because the dispersed particles of A) become fine.
- the proportion is less than 2% by mass, the size of the dispersed particles is increased, and pigment aggregation tends to occur.
- the proportion is preferably 10% by mass or more. The above ratio may be less than 100% by mass.
- the phosphoric acid ester component (A) may be finely dispersed in the mixed solvent.
- the amount of the phosphate ester component (A) used is determined by the ratio to the metal pigment used, the amount used per unit mass of the metal pigment will be described here.
- the amount of the phosphate ester component (A) used is preferably in the range of 0.2 to 3.0 times the saturated adsorption amount of the phosphate ester for the metal pigment used, and more preferably 1.0 to 2.0 times the force. More preferred! When the ratio is more than 2 times, the effect of improving the water resistance is good due to the contribution of the phosphate ester. When the ratio is less than 3.0 times, the dispersion of the phosphate ester adsorbing metal pigment hardly occurs. It is difficult for color tone deterioration to occur due to the aggregation of water.
- the saturated adsorption amount varies depending on the type of metal pigment, specific surface area, type of phosphate ester component (A) to be adsorbed, adsorption temperature, etc. Therefore, it is considered to be in the range of about 0.5 to 5% by mass.
- the saturated adsorption amount of the phosphate ester can be easily measured by the following method. Replace the solvent of the metal pigment paste with the solvent (a) that dissolves the phosphate ester well. An excess phosphate ester with respect to the expected saturation adsorption amount is dissolved in the solvent (a), and the metal pigment substituted with the solvent (a) is dispersed therein to form a slurry. The phosphate is adsorbed on the metal pigment while stirring the slurry. The slurry is filtered and the residue (ie metal pigment) is washed thoroughly with solvent (a). For the dried powder sample, for example, the phosphorus content is measured by the following method.
- the This is filtered, and the filtrate is poured into a 50 ml volumetric flask, and the inner wall of the apparatus and the residue deposits are washed with pure water.
- the volume is adjusted to 50 ml, and the phosphorus concentration is measured with ICP (ICPS-8000, manufactured by Shimadzu Corporation) at a measurement wavelength of 178 nm and converted to a phosphorus amount.
- ICP ICPS-8000, manufactured by Shimadzu Corporation
- the residue is put in a glass beaker with filter paper, and about 10 ml of 6N nitric acid and about 5 ml of 60% by mass perchloric acid are added. The solid content is completely dissolved on a sand bath at 200 ° C. Heat until clear.
- nitric acid evaporates, so nitric acid is added sequentially. After that, if heating is continued, the liquid will disappear and white smoke will be generated. Cool down when no white smoke comes out, 6N HC1 aqueous solution Add 10ml and warm to completely dissolve the contents. Measure the volume of this solution in a 50 ml volumetric flask, measure the phosphorus concentration using ICP as described above, and calculate the amount of phosphorus. Add up the phosphorus content of the filtrate and the residue, and calculate the phosphorus content from the weighed value of the powdered sample.
- the phosphoric acid ester component (A) 0.3 to: LO parts, further 1 to 6 parts, and further 2 to 5 parts
- the amount ratio of the metal pigment and the phosphate ester component (A) to the solution or dispersion, the content of the phosphate ester component (A) in the solution or the dispersion, etc. are adjusted so that the parts are in contact with each other I prefer it.
- the amount of the phosphate ester component (A) in contact with 100 parts by mass of the metal pigment is 0.3 parts by mass or more, a sufficient amount of phosphate ester can be adsorbed on the surface of the metal pigment. If it is below, excessive supply of the phosphate ester component (A) is prevented, an unnecessary increase in production cost is avoided, and aggregation of the phosphate ester adsorbing metal pigment is prevented.
- Rinorin content per unit surface area of ⁇ fat coated metal pigment is within a range of 0. 05-1. 3mg / m 2 .
- the phosphorus content is 0.05 mg / m 2 or more, the water resistance when used as a paint is excellent, and when it is 1.3 mg / m 2 or less, the production cost is not wasted. At the same time, aggregation of the phosphate-adsorbing metal pigment is prevented.
- the uniform adsorption of the phosphate ester on the surface of the metal pigment can be confirmed by, for example, infrared spectroscopy such as microinfrared spectroscopy.
- the polymerization component (B) used in the present invention a monomer and Z or oligomer having at least one polymerizable double bond are used, and further, a monomer and Z or oligomer having at least one polymerizable double bond are used. It is preferable to use a combination of at least two selected from the viewpoints of preventing aggregation due to polymerization, improving the smoothness (ie, densification) of the resin film, and improving the alkali resistance associated therewith. Specifically, for example, monomers and oligomers disclosed in JP-A No. 64-40566 are encouraged.
- the polymerization component (B) include acrylic ester and methacrylic ester such as isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxychetyl acrylate, ethoxydiethylene glycol acrylate, methoxyate triethylene glycol.
- Atalylate methoxy-polyethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxy acetyl acrylate, phenoxy polyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate 2-Hydroxypropyl Atalylate, 2-Hydroxy 1-Phenoxypropyl Atalylate, 2-Atariloy Orchicchichelic Succinic Acid, 2- Atariloy oral chichetyl phthalic acid, 2-Atearliestuloxetyl 2-hydroxyethyl phthalate, triethylene glycol ditalylate, neopentyl glycol ditalylate, 1, 6 hexanediol ditalylate, 1, 9-nonane Diol diatalylate, dimethylol-tricyclodecane diatalylate, trimethylolpropane
- the polymerization component (B) when a monomer and Z or oligomer having two or more polymerizable double bonds are used as the polymerization component (B), a resin coating layer containing a three-dimensionally crosslinked resin is formed, and the chemical resistance This is advantageous in that the characteristics are further improved.
- a polymerization slurry is prepared in which the phosphate ester adsorbing metal pigment is dispersed in a polymerization solvent as described later and the polymerization component (B) is dissolved in the polymerization solvent.
- the preparation method include a method in which a pigment slurry in which a phosphate ester adsorbing metal pigment is dispersed in a polymerization solvent is prepared, and the pigment slurry and the polymerization component (B) are mixed.
- the polymerization component (B) is added, and the monomer and Z of the polymerization component (B) are added using a radical initiator or the like.
- the oligomer is polymerized to form a resin coating layer on the surface of the metal pigment.
- the phosphate ester component (A) adsorbed on the metal pigment was preliminarily polymerized with a radical initiator or the like to form an adsorption layer having phosphate ester power on the surface of the metal pigment.
- the polymerization component (B) is added to the system, and the mixture is further polymerized with a radical initiator or the like to form a resin coating layer having a polymer strength of the polymerization component (B).
- the polymerization component (B) is added to the metal pigment adsorbed with the phosphate ester, and then the phosphate ester component (A) and the polymerization component (B) are simultaneously polymerized with a radical initiator or the like to obtain a resin.
- a coating layer may be formed!
- a copolymer with a covalent bond between the phosphate ester component (A) and the polymerization component (B) is formed, so that a more uniform and strong adsorption layer and resin coating are formed on the surface of the metal pigment. A layer is formed.
- the method of the coating step in the present invention is not limited to the force to which the method disclosed in JP-A-64-40566 can be applied.
- a polymerization solvent is used when the polymerization component (B) is polymerized.
- the polymerization solvent a solvent that does not dissolve the phosphate ester adsorbed on the surface of the metal pigment in the adsorption step may be used, and the same type of solvent as the second solvent described above may be used.
- a solution in which the solubility of the phosphate ester component (A) in lOOg for polymerization is 1 Og or less at 25 ° C is used.
- Preferable polymerization solvents include, as specific examples, aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral spirit, and aromatic hydrocarbons such as benzene, xylene, and toluene, Halogenated hydrocarbons such as chlorobenzene, trichlorobenzene, perchlorethylene, trichloroethylene, methanol, ethanol, 1 propanol, isopropyl alcohol, n-butanol, s butanol, t-butanol and other alcohols, acetone, acetyl Acetone, methyl ethyl ketone, jetyl ketone, cyclohexanone, methyl isobutyl ketone, methyl n-butyl ketone, ketones such as methyl n propyl ketone, esters such as ethyl acetate and propyl
- a polymerization initiator in particular, a radical initiator generally known as a radical generator can be used.
- a radical initiator generally known as a radical generator
- Specific examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, isobutyl baro Examples include peroxides such as oxides and methylethylketone peroxide, and azo compounds such as AIBN (azobisisobuty-tolyl).
- the blending amount of the polymerization initiator is preferably 0.1 parts by mass or more, particularly 0.5 parts by mass or more with respect to 100 parts by mass of the charged polymerization component (B). Is more preferable. Further, the blending amount is preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the blending amount of the polymerization initiator is 0.1 parts by mass or more, it is preferable in that the polymerization reaction can be surely progressed and a predetermined amount of the resin film can be easily formed.
- the blending amount is 10 parts by mass or less, the rapid progress of the polymerization can be prevented, and the generated polymer can be surely adsorbed to the metal pigment particles, and the viscosity of the entire system due to the generation of free polymer particles. This is preferable in that rapid rise and solidification can be prevented.
- the temperature of the polymerization reaction is determined by the type of polymerization initiator used.
- the half-life of the polymerization initiator is uniquely determined by the temperature, and is preferably a temperature at which the half-life of the polymerization initiator is 5 minutes or more, particularly preferably a temperature force of 15 minutes or more.
- the temperature is preferably such that the half-life of the polymerization initiator is 20 hours or less, and more preferably 10 hours or less.
- the half-life is 60, 70, 80, 90. C is 22, 5, 1. 2 0.3 hours, respectively, and 70 to 90 ° C is a more preferable temperature range.
- the polymerization reaction is carried out at a temperature at which the half-life of the polymerization initiator is 20 hours or less, the polymerization reaction does not progress so much that it is difficult to cause problems.
- the polymerization reaction When the polymerization reaction is carried out at a temperature such that the period is 5 minutes or more, the rapid progress of the polymerization reaction is prevented, and the polymer produced is adsorbed to the metal pigment particles reliably, resulting in the formation of free polymer particles. This is preferred because it prevents sudden increase in viscosity and coagulation of the entire system.
- the coating step it is advantageous to carry out the polymerization reaction in an inert gas atmosphere such as nitrogen, helium or argon in order to increase the polymerization yield.
- an inert gas atmosphere such as nitrogen, helium or argon
- the present invention is also a resin-coated metal pigment having a metal pigment, a phosphate ester layer, and a resin-coated layer that covers the metal pigment via the phosphate ester layer,
- the phosphoric ester layer is composed of phosphate mono- and Z- or diesters having radically polymerizable double bonds.
- the phosphorus content per unit surface area of the resin-coated metal pigment is 0.05 to L: 3 mg
- About ⁇ coated metal pigment is within the range of zm 2.
- the resin coating metal pigment Since the phosphoric acid ester layer is formed on the surface of the metal pigment, and the resin coating layer is further formed, the resin coating metal pigment has good water resistance when it is used as a paint. When given as a coating film, good chemical resistance is given.
- the phosphate ester layer can be formed, for example, by a method such as the adsorption step described above, and the resin coating layer can be formed, for example, by a method such as the above-described coating step. I'll do it.
- the above resin coating layer contains a three-dimensionally crosslinked resin.
- good chemical resistance can be imparted by the coating film.
- the presence of three-dimensionally crosslinked resin in the resin coating layer can be confirmed, for example, by a method such as a dissolution extraction test using various solvent species.
- the resin-coated metal pigment of the present invention can be used by blending it with a known or conventional water-based paint.
- a water-based paint containing the above-mentioned resin-coated metal pigment and a binder can be preferably exemplified. These paints may be used by mixing two or more liquids that are mixed in a one-component case, or may have a good reaction.
- the water-based paint containing the resin-coated metal pigment of the present invention can contain other pigments and dyes according to the target hue. However, it is desirable to use the pigment as long as it does not impair the metallic feel of the pigment of the present invention.
- the binder is not particularly limited as long as it is a commonly used noinder, but an emulsion binder is preferably exemplified.
- an emulsion binder it is possible to use natural or synthetic polymers, oligomers, prepolymers and the like.
- These paints can contain various additives as required. Examples of additives include surfactants, stabilizers, antifungal agents, plasticizers, pigment wetting agents, pigment dispersants, flow regulators, leveling agents, antifungal agents, and UV absorbers. And so on.
- a resin-coated metal pigment paste was dispersed in about 10 g of normal hexane and filtered. The residue was thoroughly washed with normal hexane on a filter, spread on a vat, and dried at 80 ° C. for 1 hour to obtain a powdery sample.
- About 500 g of the powdery soy sauce sample was placed in a 500 ml plastic container and weighed precisely (the precision value at this time was a).
- the contents of the above-mentioned plastic container were filtered with a glass fiber filter that was precisely weighed in advance (the accurately weighed value at this time was b). After thoroughly washing the residue with pure water on the glass fiber filter paper, it is filtered, and the glass fiber filter and the residue are intensively weighed together and put into another plastic container (the exact balance value at this time) And the residue adhering to the glass fiber filter side wall was washed out with pure water into a plastic container. After drying the contents of the plastic container for 1 kg in an oven at 105 ° C, weigh it precisely (the exact balance value at this time is d).
- the specific surface area of the metal pigment coated with the resin or the resin was measured using a fully automatic specific surface area meter Macsorb HM model-1208 manufactured by MOUN TECH. About 80% of the powdered sample prepared above was filled in a dedicated measurement container and precisely weighed. Enter the weighed value into the measuring instrument. Degas at 350 ° C for 30 minutes for non-grease-coated metal pigments at 250 ° C for 30 min. Measured with a mixed gas of 70 vol% helium.
- nitric acid was evaporated, so nitric acid was added successively. After that, when heating was continued, the liquid content disappeared and white smoke was generated. When no white smoke was emitted, the mixture was cooled, and 10 ml of 6N HC1 aqueous solution was added and heated to completely dissolve the contents. This solution was made up to volume in a 50 ml volumetric flask and the phosphorus concentration was measured using ICP in the same manner as described above to calculate the phosphorus amount. The phosphorus content of the filtrate and the residue was summed, and the phosphorus content was calculated from the weighed value of the powder sample.
- Resin-coated metal pigment is a constant temperature, polypropylene glycol monomethyl ether: 0.
- IN KOH aqueous solution 1: 1 (volume ratio) mixed in an alkaline solution that also has a mixed solvent power.
- the amount of hydrogen gas generated was measured over time.
- the horizontal axis is Log (elapsed time) and the vertical axis is the gas generation rate.
- the straight line in the region where the gas generation rate is stable is extrapolated to zero gas generation rate, and the gas generation start time LogT is obtained. . Since the gas generation start time depends on the particle size of the metal pigment, in order to correct this, the gas generation start time of the metal pigment as the raw material is measured (this is referred to as LogT ′), and the following formula:
- the amount of the sample added to the alkaline solution was 0.09 g in terms of metal content.
- the amount of hydrogen gas generated over time is measured, so it is necessary to add the sample instantaneously, and immediately close the system immediately after the addition to collect the generated gas. is there . Therefore, the sample was made into a slurry dispersed in propylene glycol monomethyl ether. Then, the slurry was added with lml with a micropipette, and the slurry concentration was adjusted so that 0.01 g of the metal was contained in the lml of the added slurry.
- a sample slurry was prepared as follows.
- FIG. 1 is a diagram showing an outline of the apparatus used for measuring the hydrogen gas generation amount.
- a 100 ml glass screw bottle sealed with screw cap 12 is used as reaction vessel 11.
- a two-way cock 13 made of Teflon (registered trademark) is attached to the screw cap 12 so that the tip of the micropipette tip can be inserted.
- the whole system is kept at a constant temperature (40 ° C) by a dry screwdriver 14 with a stirrer, and the reaction solution is constantly stirred by a stirrer tip.
- the two-way cock 13 is closed at the same time as the sample is introduced, and the system is closed.
- the hydrogen gas generated from the reaction tank reaches the water tank 17 through the Teflon (registered trademark) tube 15 and pushes up the water in the water tank. Since the pushed-up water is poured into the graduated cylinder 19 through the Teflon (registered trademark) tube 18, the amount of the generated hydrogen gas can be measured by measuring the volume of water in the graduated cylinder.
- the reaction vessel 11 was filled with 50 ml of 0. IN KOH aqueous solution and 50 ml of propylene glycol monomethyl ether with a whole pipette, and a stirrer chip was placed and set in a dry bath 14 with a stirrer. After inserting a thermocouple from the two-way cock 1 3 and confirming that the internal temperature reached 40 ⁇ 0.5 ° C, use ⁇ 7610N '' manufactured by Toyo Aluminum Co., Ltd. Lml of the prepared slurry was charged into the reaction vessel 11 with a micropipette. Simultaneously with the end of charging, the two-way cock 13 was closed, the stopwatch was started, and the elapsed time and gas generation amount were recorded.
- Fig. 2 shows the relationship between Log (elapsed time) (seconds) measured by the apparatus shown in Fig. 1 and the amount of gas generated.
- the plot where the horizontal axis is Log (elapsed time) and the vertical axis is the gas generation rate is almost on a straight line.
- the gas generation start time LogT was defined as the intersection with the X axis.
- Figure 2 shows an example of using the same sample and changing the amount of sample added by changing the concentration of the slurry to be added.
- the gas generation rate depends on the amount of sample added.
- the point LogT where the straight line is extrapolated to zero gas generation amount does not depend on the amount of sample added. Therefore, it can be seen that the amount of sample-added soot does not affect the data unless it greatly deviates from 0.09 g of aluminum. As a result of repeated reproducibility, it was found that the LogT error in this measurement method is about ⁇ 0.02.
- the value of LogT depends on the particle size of the metal pigment.
- the specific surface area generally increases, the contact area with the alkali increases, and the gas generation start time tends to be shortened.
- the effect of the particle size of the metal pigment must be corrected. Therefore, in each Example and each Comparative Example, the gas generation start time of the aluminum pigment as the raw material was measured (this is LogT ′), and the following equation:
- the alkali resistance was evaluated. That is, the larger ⁇ LogT, the better the alkali resistance.
- the case where A LogT was 0.1 or more was evaluated as good, and the case where it was less than 0.1 was evaluated as bad.
- Aqueous paint was prepared using the sample paste of each example and each comparative example, 200 g of this aqueous paint was filled in a glass container, and left in a 40 ° C circulating thermostatic water bath to generate hydrogen gas. Was measured.
- the water resistance was evaluated by the amount of gas generated after 2 days of immersion in a constant temperature water bath. The case where the amount of gas generated after 2 days of immersion in the constant temperature water bath was less than 5 ml was evaluated as good, and the case of 5 ml or more was evaluated as poor.
- Pigment paste (X) g equivalent to 7.5g of the amount of cocoon-coated metal pigment in a plastic container Then, butyl cellosolve (15— (X)) g was added and mixed well with a glass rod to make it uniform. Further, 8.0 g of N-methylpyrrolidone and 28. Og of pure water were sequentially added, and the mixture was stirred and homogenized in the same manner. To this slurry, 140 g of acrylic water-based emulsion (E-208, Mitsui Chemicals, Inc.) was added and stirred for 10 minutes with a stirrer and dispersed to obtain a water-based paint. P H of the aqueous coating composition was 7.56.
- the prepared water-based paint was spray-coated on a plastic coating plate.
- the obtained spray-coated plate was dried at room temperature for about 5 minutes, and the spray-coated plate was baked at 60 ° C. for 20 minutes to obtain a coated plate. At this time, coating was performed so that the thickness of the coating film was 10 to 20; ⁇ ⁇ .
- Aluminum paste containing aluminum pigment as metal pigment (Toyo Aluminum Co., Ltd. 7640NS non-volatile content 65.1 mass%, average particle size 16 m, specific surface area 5.5 mV g) 420 g methylethylketone (hereinafter referred to as MEK) Disperse in 640 g and filter.
- MEK methylethylketone
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- the amount of non-volatile components of this paste was 48.3 mass%, and the amount of coated resin for the aluminum content of 100 g was 11.3 g.
- the resin-coated aluminum pigment in which this paste was powdered contained 0.29% by mass of phosphorus. From the measurement of the specific surface area, the specific surface area of the resin-coated aluminum pigment is 8.2 m 2 Zg, and when converted per unit surface area, it contains 0.36 mg / m 2 of phosphorus.
- Aluminum paste containing aluminum pigment as metal pigment (Toyo Aluminum Co., Ltd. 1440YL, nonvolatile content 71.0% by mass, average particle size 31 m, specific surface area 1.7 m 2 / g) 420 g MEK640 g [Disperse 3 ⁇ 4
- 400 g of MEK was added to the filter paste, and all the solvent contained in the paste was replaced with MEK.
- the resulting paste (455.8 g) was charged in a mixer, kneaded for 10 minutes to homogenize, and the nonvolatile component was measured.
- the nonvolatile component was 64.6% by mass.
- the kneader mixer will be filled with 288. Og aluminum pigment.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- the non-volatile component of this paste was 77.3 mass%, and the amount of the coated resin with respect to 1 OOg of aluminum was 3.8 g.
- the resin-coated aluminum pigment obtained by pulverizing this paste contained 0.10% by mass of phosphorus.
- Specific table The surface area measurement ability of the resin-coated aluminum pigment is 2. Om 2 Zg. When converted to unit surface area, it contains 0.49 mg / m 2 of phosphorus.
- Aluminum paste containing aluminum pigment as metal pigment (Toyo Aluminum Co., Ltd. 5680NS, nonvolatile content 70.8 mass%, average particle size 8.7 / ⁇ ⁇ , specific surface area 10.4m 2Zg) 420g was dispersed in MEK640g After filtration, MEK40 Og was further added to the filter paste, and all solvents contained in the paste were replaced with MEK.
- the paste (449.5 g) thus obtained was filled in a mixer, kneaded for 10 minutes to homogenize, and the nonvolatile component was measured.
- the nonvolatile component was 64.1% by mass.
- the kneader mixer is filled with 281.7 g of aluminum pigment.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- the non-volatile component of this paste was 45.7% by mass, and the amount of the coated resin with respect to 100 g of aluminum was 25.2 g.
- the resin-coated aluminum pigment obtained by pulverizing this paste contained 0.48% by mass of phosphorus.
- the specific surface area measurement ability of the resin-coated aluminum pigment is 15. Om 2 Zg. When converted to unit surface area, it contains 0.32 mg / m 2 of phosphorus.
- Example 2 420 g of the same aluminum paste as in Example 1 was dispersed in MEK 640 g and filtered, and 400 g of MEK was further added to the filtered paste, and all the solvent contained in the paste was replaced with MEK.
- Og was charged into a -1 mixer and kneaded for 10 minutes to homogenize, and the nonvolatile component was measured. As a result, the nonvolatile component was 59.5% by mass.
- the Ader mixer is filled with 264.2 g of aluminum pigment.
- the non-volatile component of the phosphate ester adsorbing metal pigment paste adsorbing the 2-methacryloyllochethylacetic acid phosphate was 56.7% by mass.
- the amount of phosphate added to aluminum is 0.5% by mass, which is 0.9 mgZm 2 in terms of unit surface area.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- the non-volatile component of this paste was 55.7% by mass, and the amount of coated resin with respect to the aluminum content lOOg was 11. Og.
- the resin-coated aluminum pigment obtained by pulverizing this paste contained 0.06% by mass of phosphorus.
- the specific surface area measurement force is 7. Om 2 Zg, and the specific surface area of the resin-coated aluminum pigment contains 0.09 mg / m 2 of phosphorus when converted per unit surface area.
- Example 1 400 g of the same aluminum paste as in Example 1 was dispersed in 640 g of cyclohexanone and filtered, and 400 g of cyclohexanone was further added to the filter paste, and all the solvent contained in the paste was replaced with cyclohexanone.
- the obtained paste 410.Og was filled in a kneader mixer, kneaded for 10 minutes to homogenize, and the nonvolatile component was measured.
- the nonvolatile component was 54.2% by mass.
- the kneader mixer is filled with 216.8 g of aluminum pigment.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- Nonvolatile component of the paste is 52.4 wt 0/0, coated ⁇ amount to aluminum content 100g was 10. 2 g.
- the resin-coated aluminum pigment obtained by pulverizing this paste contained 0.17% by mass of phosphorus. From the specific surface area measurement, the specific surface area of the resin coated aluminum pigment is 7.0 m 2 Zg and contains 0.24 mg / m 2 of phosphorus per unit surface area.
- Example 2 In a 1 liter separable flask, 115.2 g of the same aluminum paste as in Example 1 and 356.0 g of mineral spirit were added, and the mixture was stirred while introducing nitrogen gas, so that the aluminum face was uniformly dispersed. Same as Example 1 2-Metataliloylokischeyl Acetic Acid Phosphate 1. A solution of 5 g in MEK 36.5 g was slowly added to the stirred slurry over 20 minutes using a dropping funnel. did. At this point in time, it was confirmed that 2-methacryloyloxy shetilt acid phosphate was finely dispersed in the slurry. Further, stirring of the slurry here was continued for 40 minutes to adsorb the phosphate ester to the aluminum pigment.
- the temperature of the system was raised to 80 ° C, 7.5 g of trimethylolpropane trimetatalylate was added, and then a solution of 0.75 g of azobisisobutyric-tolyl (reagent) dissolved in 7.6 g of MEK was added. Then, polymerization was carried out at 80 ° C. for 5 hours to coat the resin.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment as a resin-coated metal pigment.
- Nonvolatile component of the paste is 58.4 wt 0/0, coating to an aluminum content 100g
- the amount of greaves was 11.7 g.
- the resin-coated aluminum pigment obtained by pulverizing this paste contained 0.27% by mass of phosphorus. From the specific surface area measurement, the specific surface area of the resin-coated aluminum pigment is 7.6 m 2 / g, and when converted to unit surface area, it contains 0.335 mg / m 2 of phosphorus.
- This comparative example was performed by a method according to Example 1 of Japanese Patent Publication No. 01-049746.
- the phosphate ester was not adsorbed to the metal pigment, and only the resin coating was performed.
- To a 1 liter separable flask 115.2 g of the same aluminum paste as in Example 1 and 440. Og of mineral spirit were added and stirred while introducing nitrogen gas, and the temperature of the system was raised to 80 ° C.
- 0.38 g of acrylic acid manufactured by Osaka Organic Chemical Industry Co., Ltd.
- the amount of acrylic acid added to aluminum is 0.5% by mass, which is 0.9 mg / m 2 in terms of unit surface area.
- the mixture was cooled to room temperature, filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment.
- the non-volatile component of this paste was 52.6% by mass, and the amount of coated grease for 1100 g of aluminum was 11.5 g.
- This comparative example was performed by a method according to Example 3 of the pamphlet of International Publication No. WO02Z031061.
- the resin coating was not performed on the metal pigment, and only the phosphate ester was adsorbed.
- 100 g of the same aluminum paste as in Example 1 was charged into a mixer and 20 g of 3- (2-ethylhexyloxy) propylamine was added and kneaded for 5 minutes.
- 8 g of metal molybdenum powder was added little by little to 100 g of peroxyhydrogen water containing 30% by mass of peroxyhydrogen, and the resulting solution was dissolved in 175 g of isopropyl alcohol. And kneaded at 60 ° C for 1 hour.
- This comparative example was performed by a method according to Example 10 of Japanese Patent Publication No. 01-049746.
- 115.2 g of the same aluminum paste as in Example 1 and 399.8 g of mineral spirit were added and stirred while introducing nitrogen gas, and the temperature of the system was raised to 80 ° C. .
- 0.39 g of 2-methacryloyloxetyl acetate phosphate as in Example 1 was added, and stirring was continued at 80 ° C. for 30 minutes.
- the amount of phosphate ester added to aluminum is 0.5% by mass, which is 0.9 mgZm 2 in terms of unit surface area.
- the slurry was cooled to room temperature, filtered, and the slurry was observed. As a result, a lump of particles of about lmm was mixed, and this slurry was wet-screened using a screen with an opening of 150 ⁇ m! / ⁇ Separated the particle mass. The particle mass was then washed with hexane and air dried overnight. The obtained particle mass was 0.48 g. The slurry that passed through the screen was filtered, thoroughly washed with mineral spirits, and uniformly kneaded to obtain a paste containing a resin-coated aluminum pigment. Nonvolatile component of the paste is 50.0 wt 0/0, coated ⁇ amount to aluminum content 100g was 11.
- Aluminum pigment (Note 1) (Note 2) (Note 3> 7640NS 7640NS 7640NS Monomer species in adsorption process MP (Note 4 ) MP MP MP MP MP MP MP MP Adsorbed monomer amount (mass% / AI) 2.0 0.6 3.8 0.5 2.0 2.0 Adsorption Mo / mer (mg / m 2 ) 3.7 3.6 3.6 0.9 3.7 3.7 Resin coating S (g / 100g Al) 11.3 3.8 25.2 11.0 10.2 11.7 Specific surface area after resin coating
- Note 1 7640NS is manufactured by Toyo Aluminum Co., Ltd. (nonvolatile content: 65.1% by mass, average particle size: 16 m, specific surface area: 5.5 m 2 / g).
- 1440YL is manufactured by Toyo Aluminum Co., Ltd. (non-volatile content: 71.0% by mass, average particle size: 31 m, specific surface area: 1.7 m 2 Zg).
- 5680NS is manufactured by Toyo Aluminum Co., Ltd. (non-volatile content: 70.8% by mass, average particle size: 8.7 / ⁇ ⁇ , specific surface area: 10.4 m 2 Zg).
- MP is 2-methacryloyloxetyl acyl acid phosphate (trade name: Light Ester P-1M) manufactured by Kyoeisha KK.
- AA is acrylic acid manufactured by Osaka Organic Chemical Industry Co., Ltd.
- Comparative Example 1 From the results shown in Table 1 and Table 2, in Comparative Example 1, the resin coating layer was formed after adsorbing acrylic acid to the metal pigment, and both the alkali resistance and water resistance were sufficient. Not done.
- Comparative Example 2 the surface treatment for the purpose of imparting water resistance is not performed. Adsorption of phosphate ester and formation of the resin coating layer are not performed, and the alkali resistance is sufficient.
- the metallic pigment is The ability to perform a coating process to form a resin coating layer after contacting the phosphate ester.
- the phosphate ester is directly added to mineral spirit, which is a poor solvent for phosphate ester.
- the phosphoric acid ester is not in contact with the metal pigment in a dissolved or finely dispersed state and does not have sufficient performance in both alkali resistance and water resistance.
- an aqueous coating material with improved storage stability, particularly water resistance, and a resin-coated metal pigment for obtaining a coating film with improved chemical resistance By using an aqueous coating material for the resin-coated metal pigment of the present invention, a coating film having good chemical resistance can be obtained even when only one coating film is used.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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CN2006800406521A CN101300310B (zh) | 2005-10-31 | 2006-10-11 | 树脂被覆金属颜料及其制造方法、以及使用其的水性涂料 |
US11/991,840 US8283397B2 (en) | 2005-10-31 | 2006-10-11 | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
KR1020087008951A KR101288184B1 (ko) | 2005-10-31 | 2006-10-11 | 수지 피복 금속 안료 및 그 제조 방법, 그리고 이것을사용한 수성 도료 |
CA2622230A CA2622230C (en) | 2005-10-31 | 2006-10-11 | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
ES06811562.5T ES2546334T3 (es) | 2005-10-31 | 2006-10-11 | Procedimiento de producción de un pigmento de metal recubierto con resina |
EP06811562.5A EP1950257B1 (en) | 2005-10-31 | 2006-10-11 | PROCESS FOR PRODUCING a RESIN-COATED METAL PIGMENT |
US13/605,219 US8734908B2 (en) | 2005-10-31 | 2012-09-06 | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
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JP2005316087A JP4611176B2 (ja) | 2005-10-31 | 2005-10-31 | 樹脂被覆金属顔料の製造方法 |
JP2005-316087 | 2005-10-31 |
Related Child Applications (2)
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US11/991,840 A-371-Of-International US8283397B2 (en) | 2005-10-31 | 2006-10-11 | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
US13/605,219 Division US8734908B2 (en) | 2005-10-31 | 2012-09-06 | Resin-coated metal pigment, method for producing the same, and water base paint using the same |
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US (2) | US8283397B2 (ja) |
EP (2) | EP1950257B1 (ja) |
JP (1) | JP4611176B2 (ja) |
KR (1) | KR101288184B1 (ja) |
CN (1) | CN101300310B (ja) |
CA (1) | CA2622230C (ja) |
ES (2) | ES2661640T3 (ja) |
WO (1) | WO2007052447A1 (ja) |
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CN102449075A (zh) * | 2009-05-25 | 2012-05-09 | 东洋铝株式会社 | 表面被涂覆的金属颜料、含有该表面被涂覆的金属颜料的水基涂料和涂覆了该水基涂料的涂布制品 |
US8530049B2 (en) | 2008-09-17 | 2013-09-10 | Toyo Aluminium Kabushiki Kaisha | Resin-coated metallic pigment comprising a surface modifier at a surface portion, water-based paint containing the same, and method of manufacturing resin-coated metallic pigment |
WO2018047360A1 (ja) * | 2016-09-06 | 2018-03-15 | Dic株式会社 | 樹脂被覆アルミニウム顔料 |
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DE602007010975D1 (de) * | 2007-12-28 | 2011-01-13 | Eckart Gmbh | Pigmentzubereitung und Tintenstrahldrucktinte |
WO2011033655A1 (ja) * | 2009-09-18 | 2011-03-24 | 旭化成ケミカルズ株式会社 | 樹脂被覆金属顔料、およびその製造方法 |
CN102137891B (zh) * | 2009-11-16 | 2014-08-13 | 德谦(上海)化学有限公司 | 含磷酸酯基团的树脂及其用途 |
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JP6282752B2 (ja) | 2014-02-06 | 2018-02-21 | イー インク コーポレイション | 電気泳動粒子およびその生成のためのプロセス |
EP3050929A1 (de) * | 2015-01-28 | 2016-08-03 | Eckart GmbH | Beschichtete Pigmente, Verfahren zu deren Herstellung und deren Verwendung, Beschichtungsmittel und Gegenstand |
CN111100480B (zh) * | 2016-03-30 | 2022-06-10 | 埃卡特有限公司 | 用于粉末涂漆的涂覆有机粘合剂的效应颜料、用于生产所述涂覆的效应颜料的方法及其用途 |
CN109415576B (zh) * | 2016-09-06 | 2022-02-25 | Dic株式会社 | 树脂被覆无机或金属颜料 |
WO2018047359A1 (ja) | 2016-09-06 | 2018-03-15 | Dic株式会社 | 樹脂被覆無機又は金属顔料 |
JP6436250B2 (ja) * | 2016-12-01 | 2018-12-12 | Dic株式会社 | 樹脂被覆金属顔料 |
JP6384624B1 (ja) * | 2016-12-01 | 2018-09-05 | Dic株式会社 | 樹脂被覆金属顔料 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58141248A (ja) * | 1982-02-15 | 1983-08-22 | Toyo Alum Kk | 着色メタリツク顔料及びその製造方法 |
JPS62253668A (ja) * | 1985-09-07 | 1987-11-05 | Asahi Kasei Metals Kk | 新規な樹脂被覆金属顔料及びその製造方法 |
WO1996038506A1 (fr) * | 1995-05-30 | 1996-12-05 | Asahi Kasei Metals Limited | Nouveau pigment metallique enduit de resine et matiere d'enduction metallique contenant le pigment |
JP2000044835A (ja) * | 1998-07-27 | 2000-02-15 | Asahi Chem Ind Co Ltd | 樹脂被覆金属顔料およびそれを用いたメタリック塗料 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4750940A (en) * | 1985-09-07 | 1988-06-14 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and a process for producing the same |
JPS6281460A (ja) | 1985-10-04 | 1987-04-14 | Showa Arumipaudaa Kk | 合成樹脂被覆金属粉末及びその製造法 |
JPS6440566A (en) | 1987-08-07 | 1989-02-10 | Toyo Aluminium Kk | Aluminum flakes with both high corrosion resistance and gloss |
JPS6449746A (en) | 1987-08-19 | 1989-02-27 | Mitsubishi Motors Corp | Power transmission |
JP2931902B2 (ja) | 1988-10-31 | 1999-08-09 | 旭化成メタルズ株式会社 | 水性メタリツク塗料用顔料組成物 |
JPH0249076A (ja) * | 1989-05-02 | 1990-02-19 | Asahi Kasei Metals Kk | メタリック塗料 |
JP3200473B2 (ja) | 1992-08-05 | 2001-08-20 | 東洋アルミニウム株式会社 | アルミニウム顔料 |
EP1256603B1 (en) | 2000-10-13 | 2011-12-07 | Toyo Aluminium Kabushiki Kaisha | Aluminum pigment, process for its production and resin compositions containing the same |
JP4684429B2 (ja) * | 2001-02-02 | 2011-05-18 | 旭化成メタルズ株式会社 | 新規なアルミニウム顔料 |
EP1655349B1 (en) * | 2003-07-18 | 2009-10-28 | Toyo Aluminium Kabushiki Kaisha | Flake pigment, coating material and powder coating composition each containing the same, and surface-treating agent for flaky particle for use therein |
JP4485171B2 (ja) | 2003-11-14 | 2010-06-16 | 昭和アルミパウダー株式会社 | 樹脂被覆アルミニウム顔料 |
JP2005240013A (ja) * | 2004-01-30 | 2005-09-08 | Asahi Kasei Chemicals Corp | 配向性に優れた自動車用メタリック塗料組成物 |
-
2005
- 2005-10-31 JP JP2005316087A patent/JP4611176B2/ja active Active
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- 2006-10-11 EP EP06811562.5A patent/EP1950257B1/en active Active
- 2006-10-11 CA CA2622230A patent/CA2622230C/en active Active
- 2006-10-11 ES ES14169432.3T patent/ES2661640T3/es active Active
- 2006-10-11 WO PCT/JP2006/320255 patent/WO2007052447A1/ja active Application Filing
- 2006-10-11 KR KR1020087008951A patent/KR101288184B1/ko active IP Right Grant
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-
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- 2012-09-06 US US13/605,219 patent/US8734908B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58141248A (ja) * | 1982-02-15 | 1983-08-22 | Toyo Alum Kk | 着色メタリツク顔料及びその製造方法 |
JPS62253668A (ja) * | 1985-09-07 | 1987-11-05 | Asahi Kasei Metals Kk | 新規な樹脂被覆金属顔料及びその製造方法 |
WO1996038506A1 (fr) * | 1995-05-30 | 1996-12-05 | Asahi Kasei Metals Limited | Nouveau pigment metallique enduit de resine et matiere d'enduction metallique contenant le pigment |
JP2000044835A (ja) * | 1998-07-27 | 2000-02-15 | Asahi Chem Ind Co Ltd | 樹脂被覆金属顔料およびそれを用いたメタリック塗料 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1950257A4 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8530049B2 (en) | 2008-09-17 | 2013-09-10 | Toyo Aluminium Kabushiki Kaisha | Resin-coated metallic pigment comprising a surface modifier at a surface portion, water-based paint containing the same, and method of manufacturing resin-coated metallic pigment |
CN102449075A (zh) * | 2009-05-25 | 2012-05-09 | 东洋铝株式会社 | 表面被涂覆的金属颜料、含有该表面被涂覆的金属颜料的水基涂料和涂覆了该水基涂料的涂布制品 |
US8642681B2 (en) | 2009-05-25 | 2014-02-04 | Toyo Aluminium Kabushiki Kaisha | Surface-coated metallic pigment, water base paint containing the same, and coated product to which water base paint has been applied |
CN102449075B (zh) * | 2009-05-25 | 2015-05-20 | 东洋铝株式会社 | 表面被涂覆的金属颜料、含有该表面被涂覆的金属颜料的水基涂料和涂覆了该水基涂料的涂布制品 |
WO2018047360A1 (ja) * | 2016-09-06 | 2018-03-15 | Dic株式会社 | 樹脂被覆アルミニウム顔料 |
JPWO2018047360A1 (ja) * | 2016-09-06 | 2019-03-07 | Dic株式会社 | 樹脂被覆アルミニウム顔料 |
Also Published As
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ES2661640T3 (es) | 2018-04-02 |
CN101300310A (zh) | 2008-11-05 |
EP1950257A4 (en) | 2010-06-16 |
KR20080056211A (ko) | 2008-06-20 |
US8283397B2 (en) | 2012-10-09 |
EP1950257A1 (en) | 2008-07-30 |
KR101288184B1 (ko) | 2013-07-18 |
US20090131584A1 (en) | 2009-05-21 |
JP4611176B2 (ja) | 2011-01-12 |
CA2622230A1 (en) | 2007-05-10 |
CN101300310B (zh) | 2011-09-21 |
ES2546334T3 (es) | 2015-09-22 |
EP2784134B1 (en) | 2017-12-27 |
US8734908B2 (en) | 2014-05-27 |
EP2784134A1 (en) | 2014-10-01 |
CA2622230C (en) | 2015-03-24 |
JP2007119671A (ja) | 2007-05-17 |
EP1950257B1 (en) | 2015-07-08 |
US20120329946A1 (en) | 2012-12-27 |
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